Azo dye



V dyestufl with a nitro-benzoyl =chloride,re-

Patented Apr. 18, 1933 umrEbg -siarfs RAINALD BRIGHTMAN, or ENGLAN nss'reuon 'ro MPERIAL CHEMICAL T7 mnusrnms LIMITED; A ooRroRA'rIonoF GREATBRITM v No Drawing. Application filed June so, 1930, Serial No. 4es,ds4,"ana in Great Bm m'm 3, 192i 1 l According to this invention new azo dyestuffs which have the valuablehproperty of nuzosnaoonuoanmnz,

such as is obtained by the processes of 1.

D.R.P.2214 1' 'th 1- ,1 i i I 4- 33, and coup mg W1 one mo e 7 l pa rts of metmammofibenzoybmeta;

oule of a 2:8-, 1: 8- or 1: 5-amino-naphthol mono or di-sulphonic acid or an N-substituted or azo derivative thereofv and one molecule of a coupling componentother than 2-amino-5-naphthol-7-sulphonic acid or a derivative thereof containing a heteronuclear substituted amino group; Alternatively I may obtain certain of the same dyestufis by coupling a diazotized amino 'acetanilide or nitroaniline, or substitution product thereof, with a suitable coupling component, as indicated above (the coupling component used with diazotized amino-acetanilides should not contain an unsubstituted lor acyla ted amino group; the coupling component used with diazotized nitroanilines should not contain a nitro group nor an unsubstituted amino group), converting the azo dyestufi' thus ob,- tained, by hydrolysis or reductionl, into an amino-azo-dyestufi, treating the resultant ducing the nitro-azo dyestuifto a new aminobenzoyl azo dyestufi, and diazotizing and coupling with a coupling component, as already indicated.

The dyes may be represented by the general formula 5 5 R N=N on oounqo nif R by weight. w i 1 phonic acid or a derivative thereof containing a heteronuclear substituted-amino group. 1

Thefollowing examples illustrate the in 7 vention without "limiting it; The parts are phenylene diamine of M. P; 180 (1', are tetra- 1 'zotiz'ed with '500 I parts of 36 hydrochloric 13 acid and 138 parts ofsodium nitrite and the ice; After stirring a short time, asolution e5 containing. 337 parts of'sodium Z-PhehylamiA no-8 naphthol 6 -sulphonic fafcidpis run in and stirring is continued until coupling (agarr plete.

ha -.t w l Ewample 227 parts of m-aminobenzoyl-p-pheny1ene diamine, M. P. 150 0;, are tetra zotized with 500 parts of 36% hydrochloric acid and 138 parts of sodium nitrite-arid the solution of 'tetrazo compound is T irun into ;a cold, well stirred solution containing 319 parts 16f 11i i8- and the dyestuff precipitated by the addition of common salt. It dyes Viscose in bluish red shades. V

The dye prepared by Example II probably has the formula: -v

Ewample l I l 227 parts of p-amino-benzoyl-p-phenylenediamine, M. P. 205 G., are tetrazotized With 500 parts of 36% hydrochloric acid and 138 parts of sodium nitrite and the tetrazo solution is run with stirring into a cold solution containing 224parts of l-naphtholl-sulph'onic acid and 600 parts of sodium carbonate. After stirring'a short time a neutral solution containing 239 parts of 1: S-amino-naphtholl-sulphonic acid is added and stirring is continued until coupling is complete, the mixture being maintained cold and alkaline by the addition of further ice or sodium carbonate if required. The resulting mixture is then heated up and the dyestuff isolated by the addition of common salt. It dyes viscosesilk a reddish "violet shade.

For Example III the dye probably has the formula:

on a N'H.ooC -N=N H0 NB: 0.1%

OaNa

Emample I V .7 24:1'parts of m-amino-benzoyl-m=toluylene- I 5 diamine, M. P. 177 0., are tetrazotized with 138 parts of sodium nitrite and 500 parts of 36% hydrochloric acid. The tetrazo solution is run into a solution containing 251 parts of sodium 2-amino-8-naphthol-6-sulphonate and about 300 parts of sodium acetate crystals. The coupling mixture is kept free from mineral acidity and after stirring cold for some hours it is made alkaline by the addition of sodium carbonate and a solution of 224 parts1-naphthol-5-sulphonic acid is added. The coupling mixture is maintained alkaline andis'stirred until combination is complete when-it is heated up and the dyestutf isolated by the additionof common salt. It dyes viscose silk in bluish red shades.

For Example IV the dye probably has the formula:

Osbla Example V V i 227 parts "of m-amino-benzoyl-p-phenyltetrazo solution is stirred into a cold solution containing parts of sodium salicylate and 600 parts of sodiumcarbonate. After stirring a short time there is added a faintly alkaline solution of the monoazo dyestufl obtained by diazotizing 138 parts of p-nitroaniline and combining invacid solution with 319 parts of 1.: 8-a-Inino-napl1th0l-3:G-disulphonic acid in the known manner. The mixture is stirred until coupling is complete, it

is then heated up and the dyestufi' salted out,

by the addition of common salt. It dyes viscose silk in bluish green shades.

For Example V the dye probably has the formula: a

TABLE- 1. 2.1 1 Diamine tetrazotized First coupling componentf Pgflfiffiifiggfl "(Cwflgg g i (1) m-aminobenzoyl -m phenylenodil-naphthol--sulphonic acid g-amino-8;i1aphtho1 6sulphonic acid Brownish red (2)n1 aminobenzoyl p phenylene- .l-naphthol-i-sulphonic acid c2-pheny1amino-5-naphtho1 7 su1-. Crimson 1 diamin 1 phonicacid' m (3) Do. Salicylic acid 1:8 aminonaphthol 3:6 disu1-' Claret v phonic acid (4) Do. 1-naphtho1-4-su1phonicaci 2 phenylamino-zti naphthol 7- Blush-scarlet 1 x I 1 sulphqnicacid w (5) p aminobenzoyl -p phenylene- 2-amino-8-naphthol-fi-sulphonic' 1-amino-5-naphtho1-7-su1phonic Claret V diamine acid alk) acid A I J (6) Do. 2-amino-S-naphthol-6-su1phonic 1:8 aminonaphthol 3:6 disul- Maroon acid (acid) L l n' phonicacid (:1. A, a y (7) 1 -m-aminobenzoyl-2-methoxy- 4- o-cresotinic acid 2 benzoylamino 8 naphtha! g 6- Bluish red phenylenediamine '7: l 1Dh011i acid j; '7

Dyestuffs made from- Hydrolyzedand condensed Edi-f Y 1332 5} 'fidiamt'iied" 9 q d 1 W??? 118 .H t it you (1) 4-aminoacetanilide-3-su1phonicacld m-nitrobenzoyl chloride ,21- phenylarnine fSTPDBPlltllOlfl- 6- Gopper-i-ed; 5

l-naphthol-4-sulphonic acid sulphonic acid a Y I TABLEII'II Rd d 'di ed v 7 1:90 a e ucc azotiz andicoupled Shade onviscose Dyestufl made from Reduced and condensed Vwith fwlthfi 1 V ,rgyon (1) p-nitroanilineosulphonic acid m-nitrobenzoylchloride 1 ainino-8 naphtliol-i-slflphonic Blue l-naphthoH-sulphonic acid acid H w j" (2) p-nitroanilinesa1icylic acid Do. 1 2 lllale ilzovlamiio 5 naphthol 7- Orange brown v s p on1c aci (3) m-nitmanilinw salicylic acid pnitrobcnzoylchloride 1:8 aminonaphthol 2:4 disul- Red violet phonic acid 7 1 TABLE IV @1 Reduced, diazotized and coupled Shade onv Dyestufi made from Condensed with (1) m-amino-pcresol methylether p-nitrobenzoylchlorlda 1:8 aminonaphthol-3z6-disulphonic ('ireenish-hlue m-amino-prresol-methyl ether acid (2) p-chloraniline-o-sulphonic acid- D0. 1:8 -aminonaphthol-2:4-disulphonic Greenish-blue m-aminwp-cresoI-methylether acid It will be obvious thatthe above examples I claim: 7 1 V are furnished by way of illustration merely l. The process of making a new azo dve and that it is not the lntention that applicant stufi which comprises tetrazotizing an amino be llmlted to the exact conditions set forth benzoyl phenylene-diaminecompound, couthereln. ()bvlously many other coupllng phng the resulting tetrazo' compound with components than those specified may be ema compound of the group consisting of 2:8, ployed. Thus, as first components among 1:8, 1: 5'amino-naphthol-sulphonic acids and compounds having the structure N-substltuted and benzene azo derivatives th e NH .C H .CO.NH.C H .NH 1 er of and i h p g 90111190116111? Se r e tcd from the group conslstmg of an aro- 1t 1s intended to include alkyl substituted matic compo'und'of the benzene and a-comcompounds of the type illustrated 1n Ex- 7 pound of the naphthalene series consisting of I ample IV. In place of salicylic acid, other the napthols and their sulfonic acids, the I 120, aromatic hydroxy acids and their alkali napthylamines and their sulphonic acids,the metal salts may be employed and m place of 2 8-; 1: 8-, 1: 5-amino naphthol sulfonic the partlcular naphthol sulphonlc acids menacids and the1r N-substituted derivatives. tloned others may be substituted. 7 2. The process of making anew azov dye- As many apparent and widely dlfierent stuif which comprlsestetrazotizing a comembodlments of this mventlon may be made pound havmg the general structure without departing from the-spirit thereof, it NH O H O NH NH is to be understood that I do not limit myself 6 2 to the foregoing examples or description excoupling the result ng tetrazo compound with" cept as lndlcatedm the followlng clalms. a compound of the group consistmg of sali- 13d cylic acid, sodium salicylate, B-naphtholf- 1-naphth01-4-sulph0nic acid andl-naphthol- 5-sulphonic acidand with a compound of the group consisting of 2-pheny1amino-8-naphthol-fi-sulphonic acid, 1: S-aminO-naphthol- 2:4-disu1ph0nic acid, 1:8-amino-na htholl-sulphonic acid, '2-amino-8-naphtho -6-su1- phonic acid and the mono-azo dye resulting from combining diazotized p-nitroaniline in acid solution with 1:8-amino-naphthol-3z6- disulphonic acid.

3. dyestufi' having thegeneral formula *N?NrQ N *BT.

in which R represents an organic residue of a 2 8-, 1: 8-, or 1: 5-amino-naphthol-sulfonic acid "or an N-suhstituted or a benzene azo derivative thereof and R represents the residue of acoupling component selectedfrom the group conslstlng-of an aromatic compound of the benzene series and a compound of the naphthalene serles consisting of the naphthols and their sulfonic acids, the V naphthylamines and their sulfonic acids,

the 21 8-, 1: 8-, 1:5-amino-naphthol-su1fonic acids and their N-substituted derivatives.

In testimony whereof I have signed my name to this specification.

M V Y RAINALD BRIGHTMAN. 

